Chemical Distinction by Nuclear Spin Optical Rotation

Nuclear spin optical rotation (NSOR) arising from the Faraday effect constitutes a novel, advantageous method for detection of nuclear magnetic resonance, provided that a distinction is seen between different chemical surroundings of magnetic nuclei. Efficient first-principles calculations for isolated water, ethanol, nitromethane, and urea molecules at standard laser wavelengths reveal a range of NSOR for different molecules and inequivalent nuclei, indicating the existence of an optical chemical shift. H-1 results for H2O(l) are in excellent agreement with recent pioneering experiments. We also evaluate, for the same systems, the Verdet constants of Faraday rotation due to an external magnetic field. Calculations of NSOR in ethanol and a 11-cis-retinal protonated Schiff base imply an enhanced chemical distinction between chromophores at laser wavelengths approaching optical resonance.